U.S. patent application number 11/608508 was filed with the patent office on 2007-06-14 for composition and process for coloring wood.
This patent application is currently assigned to Osmose, Inc.. Invention is credited to Jun Zhang, Wenjin Zhang.
Application Number | 20070131136 11/608508 |
Document ID | / |
Family ID | 38138002 |
Filed Date | 2007-06-14 |
United States Patent
Application |
20070131136 |
Kind Code |
A1 |
Zhang; Wenjin ; et
al. |
June 14, 2007 |
Composition And Process For Coloring Wood
Abstract
Provided is a method for coloring and, optionally, preserving
wood and wood products. The method comprises application of pigment
dispersions, and optionally biocide dispersions, to wood such that
the wood is impregnated. A composition for coloring and,
optionally, preserving wood is disclosed, comprising dispersions of
micronized pigment and, optionally, micronized biocide.
Inventors: |
Zhang; Wenjin; (Tonawanda,
NY) ; Zhang; Jun; (Getzville, NY) |
Correspondence
Address: |
HODGSON RUSS LLP
ONE M & T PLAZA
SUITE 2000
BUFFALO
NY
14203-2391
US
|
Assignee: |
Osmose, Inc.
980 Ellicott Street
Buffalo
NY
14209
|
Family ID: |
38138002 |
Appl. No.: |
11/608508 |
Filed: |
December 8, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11299522 |
Dec 12, 2005 |
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11608508 |
Dec 8, 2006 |
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11126839 |
May 11, 2005 |
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11299522 |
Dec 12, 2005 |
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11116152 |
Apr 27, 2005 |
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11299522 |
Dec 12, 2005 |
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60570659 |
May 13, 2004 |
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60565585 |
Apr 27, 2004 |
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Current U.S.
Class: |
106/15.05 ;
106/18.3; 106/18.32; 106/18.33; 106/18.34; 106/18.35; 424/617;
424/630; 424/638; 424/642; 424/646; 424/650; 424/654; 424/657;
427/297; 428/537.1; 514/183; 514/642 |
Current CPC
Class: |
C09D 15/00 20130101;
B27K 3/005 20130101; Y10T 428/31989 20150401; B27K 3/52 20130101;
A61K 31/33 20130101; B27K 5/02 20130101; B27K 2240/20 20130101;
A61K 33/22 20130101 |
Class at
Publication: |
106/015.05 ;
106/018.3; 106/018.32; 106/018.33; 106/018.34; 106/018.35; 424/617;
424/630; 424/638; 424/642; 424/646; 424/650; 424/654; 424/657;
427/297; 428/537.1; 514/183; 514/642 |
International
Class: |
C09D 5/14 20060101
C09D005/14; C09D 5/16 20060101 C09D005/16; A61K 31/33 20060101
A61K031/33; B05D 3/00 20060101 B05D003/00; B32B 21/04 20060101
B32B021/04; A61K 33/24 20060101 A61K033/24; A01N 59/20 20060101
A01N059/20; A61K 33/34 20060101 A61K033/34; A01N 33/12 20060101
A01N033/12; A01N 59/16 20060101 A01N059/16; A61K 33/26 20060101
A61K033/26; A61K 33/22 20060101 A61K033/22 |
Claims
1. A composition for preserving wood against wood destroying
organisms and coloring the wood comprising: a) a micronized pigment
component; b) a dispersant; and c) a biocide; wherein a), and
optionally, c) comprise a particulate dispersion comprising
micronized particles, and wherein greater than 60 weight percent of
the particles present in said composition are micronized.
2. The composition of claim 1, wherein the pigment is a micronized
inorganic pigment.
3. The composition of claim 2, wherein greater than 60 weight
percent of the particles of micronized inorganic pigment have sizes
between 0.001 microns and 25 microns.
4. The composition of claim 2, wherein greater than 60 weight
percent of the particles of micronized inorganic pigment have sizes
between 0.005 to 10 microns.
5. The composition of claim 2, wherein greater than 60 weight
percent of the particles of micronized inorganic pigment have sizes
between 0.05 to 5 microns.
6. The composition of claim 2, wherein greater than 60 weight
percent of the particles of micronized inorganic pigment have sizes
between 0.05 to 1 micron.
7. The composition of claim 2, wherein the inorganic pigment
comprises a metal selected from the group consisting of iron,
copper, aluminum, calcium, zinc, titanium, cobalt, tin, nickel,
silver, silicon, chromium, barium, bismuth, carbon black, and
graphite.
8. The composition of claim 7, wherein the inorganic pigment is
selected from the group consisting of iron oxide, red iron oxide,
yellow iron oxide, black iron oxide, brown iron oxides, carbon
black, iron hydroxide, graphite, black micaceous iron oxide,
aluminum flake pigment, pearlescent pigment, calcium carbonate,
calcium phosphate, calcium oxide, calcium hydroxide, bismuth oxide,
bismuth hydroxide, bismuth carbonate, copper carbonate, copper
hydroxide, basic copper carbonate, cupric oxide, cuprous oxide,
silicon oxide, zinc carbonate, barium carbonate, barium hydroxide,
strontium carbonate, zinc oxide, zinc phosphate, zinc chromate,
barium chromate, chrome oxide, titanium dioxide, zinc sulfide,
antimony oxide, lead chrome, and a cadmium pigment.
9. The composition of claim 1, wherein the micronized pigment is an
organic pigment.
10. The composition of claim 9, wherein the micronized organic
pigment selected from the group consisting of monoazo (arylide)
pigments, disazo (diarylide) pigments, disazo condensation
pigments, benzimidazolone pigments, beta Naphthol pigments,
Naphthol pigments, metal-organic complexes, Isoindoline,
Isoindolinone, quinacridone; perylene; perinone; anthraquinone;
diketo-pyrrolo pyrrole; dioxazine; triacrylcarbonium; cobalt
phthalocyanine, copper phthalocyanine, copper semichloro- or
monochlorophthalocyanine, copper phthalocyanine, metal-free
phthalocyanine, copper polychlorophthalocyanine, phthalocyanine
blue, other phthalocyanine pigments; organic azo compound pigments;
organic nitro compound pigments; polycyclic compound pigments,
phthalocyanine pigments, quinacridone pigments, perylene pigments,
perinone pigments; diketopyrrolo-pyrrole(DPP) pigments; thioindigo
pigments; dioxazine pigments; quinophthalone pigments;
triacrylcarbonium pigments, and diaryl pyrrolopyrole pigments.
11. The composition of claim 1, wherein the dispersant is a
polymeric dispersant.
12. The composition of claim 11, wherein the polymeric dispersant
is selected from group consisting of acrylic copolymers, aqueous
solutions of copolymers having pigment affinity groups,
polycarboxylate ethers, modified polyacrylates or modified
polyacrylates having high pigment affinity, acrylic polymer
emulsions, modified acrylic polymers, poly carboxylic acid polymers
and their salts, modified poly carboxylic acid polymers and their
salts, fatty acid modified polyester, aliphatic polyether or
modified aliphatic polyether, polycarboxylate ether solutions,
phosphate esters, phosphate ester-modified polymers, polyglycol
ethers, modified polyglycol ethers, polyetherphosphate, modified
maleic anhydride/styrene copolymers, sodium polyacrylate, sodium
polymethacrylate, lignin, modified lignin and the like; modified
polyether or polyester with pigment affinic groups; fatty acid
derivatives; urethane copolymer or modified urethane copolymer,
polyetherphosphate, modified maleic anhydride/styrene copolymer,
modified polycarboxylic acids or their derivatives, acrylic
acid/maleic acid copolymers, polyvinyl pyrrolidones, modified
polyvinyl pyrrolidones, sulfonates, sulfonate derivatives,
polymeric alkoxylates or its polymeric alkoxylate derivatives, or
modified lignin.
13. The composition of claim 2, wherein the dispersant comprises
0.1 to 180% of the weight of the pigment compounds.
14. A composition as in claim 13 wherein the dispersant is
preferably in the range of from about 1 to 80% of the weight of the
pigment compounds.
15. A composition as in claim 14 wherein the dispersant is
preferably in the range of from about 5 to 60% of the weight of the
pigment compounds.
16. A composition as in claim 15 wherein the dispersant is
preferably in the range of from about 10 to 30% of the weight of
the pigment compounds.
17. The composition of claim 9, wherein the dispersant comprises 1
to 200% of the weight of the pigment compounds.
18. The composition as in claim 17, wherein the dispersant is
preferably in the range of from about 10 to 80% of the weight of
the pigment compounds.
19. The composition as in claim 18 wherein the dispersant is
preferably in the range of from about 30 to 70% of the weight of
the pigment compounds.
20. The composition of claim 1, wherein the said biocide is an
inorganic biocide.
21. The composition of claim 20, wherein the inorganic biocide
comprises a compound comprising a metal selected from the group
consisting of a compound of copper, boron, zinc, cobalt, cadmium,
silver, nickel, and tin.
22. The composition of claim 21, wherein the inorganic biocide is a
copper compound, a zinc compound or a boron compound.
23. The composition of claim 22, wherein the biocide is copper
hydroxide, copper oxide, copper carbonate, basic copper carbonate,
copper oxychloride, copper 8-hydroxyquinolate, copper
dimethyldithiocarbamate, copper omadine or copper borate.
24. The composition of claim 22, wherein the biocide is zinc oxide,
zinc phosphate, zinc borate or zinc carbonate.
25. The composition of claim 20, where the inorganic biocide is
micronized.
26. The composition of claim 1, wherein the biocide is an organic
biocide.
27. The composition of claim 26, wherein the biocide is a triazole
or an imidazole.
28. The composition of claim 27, wherein the biocide is
tebuconazole; cyproconazole; propiconazole; hexaconazole;
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole;
cis-trans-3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxol-
an-2-yl]phenyl 4-chlorophenyl ether;
(RS)-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-(trimethylsilyl)propa-
n-2-ol; or
2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazole-1-yl)-3-trimethylsi-
lyl-2-propanol.
29. The composition of claim 26, wherein the organic biocide is a
quaternary ammonium compound.
30. The composition of claim 29, wherein the quaternary ammonium
compound is selected from the group consisting of
didecyldimethylammonium chloride, didecyldimethylammonium
carbonate/bicarbonate, alkyldimethylbenzylammonium chloride,
alkyldimethylbenzylammonium carbonate/bicarbonate,
didodecyldimethylammonium chloride, didodecyldimethylammonium
carbonate/bicarbonate, didodecyldimethylammonium propionate, and
N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate.
31. The composition of claim 26, wherein the organic biocide is an
isothiazolone compound.
32. The composition of claim 31, where in the isothiazolone
compound is methylisothiazolinone, chloromethylisothiazolinone,
4,5-Dichloro-2-n-octyl-3(2H)-isothiazolone,
1,2-benzisothiazolin-3-one, or 2-octyl-3-isothiazolone.
33. The composition of claim 26, wherein the organic biocide is
synthetic pyrethroid compound.
34. The composition of claim 33, where the synthetic pyrethroid
compound is acrinathrin, allethrin, bioallethrin, barthrin,
bifenthrin, bioethanomethrin, cyclethrin, cycloprothrin,
cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin,
lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,
beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin,
cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin,
fenfluthrin, fenpirithrin, fenpropathrin, fenvalerate,
esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate,
furethrin, imiprothrin, metofluthrin, permethrin, biopermethrin,
transpermethrin, phenothrin, prallethrin, profluthrin,
pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin,
terallethrin, tetramethrin, tralomethrin, transfluthrin,
etofenprox, flufenprox, halfenprox, protrifenbute, or
silafluofen.
35. The composition of claim 26, where the organic biocide is
iodopropynyl butylcarbamate, chlorothalonil,
2-(thiocyanatomethylthio) benzothiazole; alkoxylated diamines and
carbendazim, fipronil or imidachloprid.
36. The composition of claim 26, where the organic biocide is
micronized.
37. The composition of claim 1 further comprising a resin
binder.
38. The composition of claim 1 further comprising a dye.
39. The composition of the claim 38, wherein the dye is a acid dye,
basic dye, direct dye, or reactive dye.
40. A method for coloring wood or a wood product comprising the
step of impregnating the product with the wood coloring composition
comprising: a) a pigment component; and b) a dispersant; wherein a)
comprises a dispersion of particles comprising micronized
particles, and wherein greater than 60 weight percent of the
particles present in said dispersion are micronized.
41. The method of claim 40, wherein the pigment is a micronized
inorganic pigment.
42. The method of claim 41, wherein greater than 60 weight percent
of the particles of micronized inorganic pigment have sizes between
0.001 microns and 25 microns.
43. The method of claim 41, wherein greater than 60 weight percent
of the particles of micronized inorganic pigment have sizes between
0.005 to 10 microns.
44. The method of claim 41, wherein greater than 60 weight percent
of the particles of micronized inorganic pigment have sizes between
0.05 to 5 microns.
45. The method of claim 41, wherein greater than 60 weight percent
of the particles of micronized inorganic pigment have sizes between
0.05 to 1 micron.
46. The method of claim 41, wherein the inorganic pigment comprises
a metal selected from the group consisting of iron, copper,
aluminum, calcium, zinc, titanium, cobalt, tin, nickel, silver,
silicon, chromium, barium, bismuth, carbon black, and graphite.
47. The method of claim 46, wherein the inorganic pigment is
selected from the group consisting of iron oxide, red iron oxide,
yellow iron oxide, black iron oxide, brown iron oxides, carbon
black, iron hydroxide, graphite, black micaceous iron oxide,
aluminum flake pigment, pearlescent pigment, calcium carbonate,
calcium phosphate, calcium oxide, calcium hydroxide, bismuth oxide,
bismuth hydroxide, bismuth carbonate, copper carbonate, copper
hydroxide, basic copper carbonate, cupric oxide, cuprous oxide,
silicon oxide, zinc carbonate, barium carbonate, barium hydroxide,
strontium carbonate, zinc oxide, zinc phosphate, zinc chromate,
barium chromate, chrome oxide, titanium dioxide, zinc sulfide,
antimony oxide, lead chrome, and a cadmium pigment.
48. The method of claim 40, wherein the micronized pigment is an
organic pigment.
49. The method of claim 48, wherein the micronized organic pigment
selected from the group consisting of monoazo (arylide) pigments,
disazo (diarylide) pigments, disazo condensation pigments,
benzimidazolone pigments, beta Naphthol pigments, Naphthol
pigments, metal-organic complexes, Isoindoline, Isoindolinone,
quinacridone; perylene; perinone; anthraquinone; diketo-pyrrolo
pyrrole; dioxazine; triacrylcarbonium; cobalt phthalocyanine,
copper phthalocyanine, copper semichloro- or
monochlorophthalocyanine, copper phthalocyanine, metal-free
phthalocyanine, copper polychlorophthalocyanine, phthalocyanine
blue, other phthalocyanine pigments; organic azo compound pigments;
organic nitro compound pigments; polycyclic compound pigments,
phthalocyanine pigments, quinacridone pigments, perylene pigments,
perinone pigments; diketopyrrolo-pyrrole(DPP) pigments; thioindigo
pigments; dioxazine pigments; quinophthalone pigments;
triacrylcarbonium pigments, and diaryl pyrrolopyrole pigments.
50. The method of claim 40, wherein the dispersant is a polymeric
dispersant.
51. The method of claim 50, wherein the polymeric dispersant is
selected from group consisting of acrylic copolymers, aqueous
solutions of copolymers having pigment affinity groups,
polycarboxylate ethers, modified polyacrylates or modified
polyacrylates having high pigment affinity, acrylic polymer
emulsions, modified acrylic polymers, poly carboxylic acid polymers
and their salts, modified poly carboxylic acid polymers and their
salts, fatty acid modified polyester, aliphatic polyether or
modified aliphatic polyether, polycarboxylate ether solutions,
phosphate esters, phosphate ester-modified polymers, polyglycol
ethers, modified polyglycol ethers, polyetherphosphate, modified
maleic anhydride/styrene copolymers, sodium polyacrylate, sodium
polymethacrylate, lignin, modified lignin and the like; modified
polyether or polyester with pigment affinic groups; fatty acid
derivatives; urethane copolymer or modified urethane copolymer,
polyetherphosphate, modified maleic anhydride/styrene copolymer,
modified polycarboxylic acids or their derivatives, acrylic
acid/maleic acid copolymers, polyvinyl pyrrolidones, modified
polyvinyl pyrrolidones, sulfonates, sulfonate derivatives,
polymeric alkoxylates or its polymeric alkoxylate derivatives, or
modified lignin.
52. The method of claim 41, wherein the dispersant comprises 0.1 to
180% of the weight of the pigment compounds.
53. A method as in claim 52 wherein the dispersant is preferably in
the range of from about 1 to 80% of the weight of the pigment
compounds.
54. A method as in claim 53 wherein the dispersant is preferably in
the range of from about 5 to 60% of the weight of the pigment
compounds.
55. A method as in claim 54 wherein the dispersant is preferably in
the range of from about 10 to 30% of the weight of the pigment
compounds.
56. The method of claim 48, wherein the dispersant comprises 1 to
200% of the weight of the pigment compounds.
57. The method as in claim 56, wherein the dispersant is preferably
in the range of from about 10 to 80% of the weight of the pigment
compounds.
58. The method as in claim 57 wherein the dispersant is preferably
in the range of from about 30 to 70% of the weight of the pigment
compounds.
59. The method of claim 40, wherein the wood or wood product is
additionally impregnated with a biocide, wherein 1) the composition
additionally comprises the biocide, or 2) the method additionally
comprises a step which comprises impregnation with a biocide; and
wherein the biocide impregnation step takes place prior to or after
the impregnation of the wood or wood product with the pigment.
60. The method of claim 59, wherein the biocide is an inorganic
biocide.
61. The method of claim 60, wherein the inorganic biocide comprises
a compound comprising a metal selected from the group consisting of
a compound of copper, boron, zinc, cobalt, cadmium, silver, nickel,
and tin.
62. The method of claim 61, wherein the inorganic biocide is a
copper compound, a zinc compound or a boron compound.
63. The method of claim 62, wherein the biocide is copper
hydroxide, copper oxide, copper carbonate, basic copper carbonate,
copper oxychloride, copper 8-hydroxyquinolate, copper
dimethyldithiocarbamate, copper omadine or copper borate.
64. The method of claim 62, wherein the biocide is zinc oxide, zinc
phosphate, zinc borate, or zinc carbonate.
65. The method of claim 60, where the inorganic biocide is
micronized.
66. The method of claim 59, wherein the biocide is an organic
biocide.
67. The method of claim 66, wherein the biocide is a triazole or an
imidazole.
68. The composition of claim 67, wherein the biocide is
tebuconazole; cyproconazole; propiconazole; hexaconazole;
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole;
cis-trans-3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxol-
an-2-yl]phenyl 4-chlorophenyl ether;
(RS)-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-(trimethylsilyl)propa-
n-2-ol; or
2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazole-1-yl)-3-trimethylsi-
lyl-2-propanol.
69. The method of claim 66, wherein the organic biocide is a
quaternary ammonium compound.
70. The method of claim 69, wherein the quaternary ammonium
compound is selected from the group consisting of
didecyldimethylammonium chloride, didecyldimethylammonium
carbonate/bicarbonate, alkyldimethylbenzylammonium chloride,
alkyldimethylbenzylammonium carbonate/bicarbonate,
didodecyldimethylammonium chloride, didodecyldimethylammonium
carbonate/bicarbonate, didodecyldimethylammonium propionate, and
N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate.
71. The method of claim 66, wherein the organic biocide is an
isothiazolone compound.
72. The method of claim 71, where in the isothiazolone compound is
methylisothiazolinone, chloromethylisothiazolinone,
4,5-Dichloro-2-n-octyl-3(2H)-isothiazolone,
1,2-benzisothiazolin-3-one, or 2-octyl-3-isothiazolone.
73. The method of claim 66, wherein the organic biocide is
synthetic pyrethroid compound.
74. The method of claim 73, where the synthetic pyrethroid compound
is acrinathrin, allethrin, bioallethrin, barthrin, bifenthrin,
bioethanomethrin, cyclethrin, cycloprothrin, cyfluthrin,
beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin,
lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,
beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin,
cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin,
fenfluthrin, fenpirithrin, fenpropathrin, fenvalerate,
esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate,
furethrin, imiprothrin, metofluthrin, permethrin, biopermethrin,
transpermethrin, phenothrin, prallethrin, profluthrin,
pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin,
terallethrin, tetramethrin, tralomethrin, transfluthrin,
etofenprox, flufenprox, halfenprox, protrifenbute, or
silafluofen.
75. The method of claim 66, where the organic biocide is
iodopropynyl butylcarbamate, chlorothalonil,
2-(thiocyanatomethylthio) benzothiazole; alkoxylated diamines and
carbendazim, fipronil or imidachloprid.
76. The method of claim 66, where the organic biocide is
micronized.
77. The method of claim 40 further comprising a resin binder.
78. The method of claim 40 further comprising a dye.
79. The method of claim 78, wherein the dye is an acid dye, basic
dye, direct dye, or reactive dye.
80. Wood or a wood product having distributed through at least a
portion thereof a composition comprising: a) a dispersion of
pigment particles; and b) a dispersant, wherein greater than 60
weight percent said particles are micronized.
81. Wood or a wood product as in claim 80 wherein the wood is a
coniferous wood.
82. Wood or a wood product as in claim 80 wherein said composition
additionally comprises a particulate biocide.
83. Wood or a wood product as in claim 80 wherein said particulate
biocide comprises copper or a copper compound.
84. Wood or a wood product as in claim 83 wherein greater than 60
weight percent of the pigment and biocide particles present in said
composition are micronized.
85. Wood or a wood product as in claim 84 wherein said biocide
comprises one or more inorganic and/or organic biocides selected
from the group consisting of tebuconazole, bifenthrin, dimethyl
didecyl ammonium carbonate/bicarbonate and dimethyl didecyl
ammonium chloride, propiconazole, cyproconazole,
4,5Dichloro-2-N-Octyl-4-isothiazolin-3-one (rh-287) imidacloprid,
fipronil, permethrin, and cypromethrin.
86. Wood or a wood product as in claim 84, further comprising a
resin binder.
87. Wood or a wood product as in claim 84 wherein a) comprises one
or more organic pigments.
88. Wood or a wood product as in claim 84 wherein said dispersant
comprises one or more polymers selected from the group consisting
of a modified maleic anhydride/styrene copolymer, acrylic
acid/maleic acid copolymer and combinations thereof.
89. Wood or a wood product as in claim 88 wherein the dispersant is
preferably in the range of from about 1 to 200% of the weight of
the pigment compounds.
90. Wood or a wood product as in claim 88 wherein the dispersant is
preferably in the range of from about 10 to 80% of the weight of
the pigment compounds.
91. Wood or a wood product as in claim 88 wherein the dispersant is
preferably in the range of from about 30 to 70% of the weight of
the pigment compounds.
92. Wood or a wood product as in claim 84 wherein a) comprises one
or more inorganic pigments.
93. Wood or a wood product as in claim 92 wherein said dispersant
comprises one or more polymers selected from the group consisting
of a polycarboxylate ether, a modified poly carboxylic acid
polymers or its salts, a modified polyether or polyester with
pigment affinic groups.
94. Wood or a wood product as in claim 93 wherein the dispersant is
preferably in the range of from about 1 to 200% of the weight of
the pigment compounds.
95. Wood or a wood product as in claim 93 wherein the dispersant is
preferably in the range of from about 0.1 to 180% of the weight of
the pigment compounds.
96. Wood or a wood product as in claim 93 wherein the dispersant is
preferably in the range of from about 1 to 80% of the weight of the
pigment compounds.
97. Wood or a wood product as in claim 93 wherein said dispersant
is preferably in the range of from about 5 to 60% of the weight of
the pigment compounds.
98. Wood or a wood product as in claim 93 wherein said dispersant
is preferably in the range of from about 10 to 30% of the weight of
the pigment compounds.
99. Wood or a wood product as in claim 80 wherein a) comprises a
pigment selected from the group consisting of carbon black,
graphite, iron oxide, black micaceous iron oxide, iron hydroxide,
zinc oxide, titanium oxide, titanium dioxide, aluminum oxide and
aluminum hydroxide.
100. Wood or a wood product as in claim 99 wherein a) comprises
iron oxide selected from the group consisting of red iron oxides,
yellow iron oxides, black iron oxides and brown iron oxides.
101. Wood or a wood product as in claim 80 wherein a) comprises one
or more organic pigments yellow, red, orange, green, blue, black or
brown.
102. Wood or a wood product as in claim 80 having a dye distributed
through at least a portion thereof.
Description
[0001] This application is a continuation-in-part of U.S.
Non-provisional application No. 11/299,522 filed on Dec. 12, 2005,
which is a continuation-in-part of U.S. Non-provisional application
No. 11/126,839 filed on May 11, 2005, which claims priority to U.S.
Provisional application No. 60/570,659 filed on May 12, 2004, the
disclosure of which is incorporated herein by reference; and is
also a continuation-in-part of U.S. Non-provisional application No.
11/116,152 filed on Apr. 27, 2005, which claims priority to U.S.
Provisional application No. 60/565,585 filed on Apr. 27, 2004, the
disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] This invention relates to a composition and method for both
coloring and, optionally, preserving cellulosic products, such as
wood, to improve their outdoor weathering properties and their
resistance to rot- and decay-causing organisms or environmental
agents. More particularly, the invention relates to a composition
and method whereby coloring and preserving of wood may be
accomplished in a single application step, or sequentially, in two
separate application steps, which may be performed in either
order.
BACKGROUND OF THE INVENTION
[0003] Wood which is both colored and preserved is used extensively
in the construction industry in applications including siding,
fencing, and decking. It has long been desirable to produce wood
products that have an aesthetically pleasing appearance and good
outdoor weathering properties, and yet have resistance to attack by
wood destroying agencies such as fungi, bacteria and insects.
[0004] Untreated wood, when exposed to an outdoor environment, is
subject to bio-deterioration due to attack by decay fungi and
insects. In addition, untreated wood is subject to
photo-degradation which will cause yellowing, fading, graying and,
over time, a darkening of the wood surface.
[0005] Traditionally, wood preservative solutions used by wood
preservation industry to impart resistance to fungal and insect
attack contain metals or metal complexes. Examples are chromated
copper arsenate (CCA), alkaline copper quaternary ammonium
compounds (ACQ) and others, such as those described in American
Wood Preservers' Association Standards-2005. These preservative
systems not only provide decay and termite resistance, but also
provide protection against photo-degradation due to the presence of
metal or metal complexes which can act as absorbers and/or blockers
of ultraviolet radiation. Unfortunately, many of the metal-based
preservatives impart an undesirable color to the wood.
[0006] Thus, the wood preservation industry is increasingly
interested in non-traditional preservatives, such as organic
preservatives or non-metal based preservatives. However, such
preservatives generally weather poorly upon exposure to sunlight.
In fact, wood which has been treated with these preservatives can
weather as poorly as wood which has not undergone treatment.
[0007] Thus colorants have been used in conjunction with
preservatives in an attempt to improve weathering properties of
preserved wood.
[0008] One technique currently used to color wood is to paint the
surface of the wood with oil or water based pigment paint coating.
However, paint often will not adhere to preservative-treated wood,
resulting in blistering or flaking of the coating in a short period
of time.
[0009] Additionally, a critical failure of this and other coating
methods is that they provide surface coloration which may wear
away, or lose color due to dent or scratches or other physical
damage to the surface, requiring additional treatment or servicing
if long term weathering is desired.
[0010] Another technique currently used to color wood is the
addition of water soluble dyes to the preservative solution thereby
imparting color to treated wood products. However, water soluble
dyes, such as acid dyes or cationic dyes, generally have poor
lightfastness, generally fading or decomposing upon exposure to
sunlight, particularly ultra violet (UV) wavelengths.
[0011] In view of the many shortcomings of the current methods of
coloring and preserving wood, it is desirable to have a coloring
and preserving system that provides an aesthetically pleasing
appearance, long-term weathering performance, and resistance to
biodeterioration. It is also desirable to have a coloring and
preserving process which can, if desired, be completed in a single
application step.
SUMMARY OF THE INVENTION
[0012] Provided are wood colorant compositions that can be used
with inorganic and organic wood preservatives. The colorant
compositions comprise dispersions of inorganic and/or organic
pigments in the form of micronized particles. The composition
optionally additionally comprises inorganic and/or organic
biocides, which may be present as dispersions, emulsions or in
solution.
[0013] The compositions of the present invention can be used to
color wood or in additional embodiments, to simultaneously color
and preserve wood. In the art, "wood preservatives" and "biocides"
are sometimes identified with inorganic (metal or metal salt) or
organic compounds, respectively. However, herein, the terms
"preservative" and "biocide" are used interchangeably to refer to
both organic and inorganic compounds.
[0014] In one embodiment, the composition comprises a micronized
inorganic pigment. In another embodiment, the composition comprises
a micronized organic pigment. In yet another embodiment, the
composition comprises one or more micronized inorganic and/or
organic pigments and a micronized biocide. In further embodiments,
the composition comprises one or more micronized inorganic and/or
organic pigments and one or more inorganic and/or organic biocides.
Dyes including acid dyes, basic dyes and direct dyes can optionally
be added to the composition to further enhance the aesthetic
appearance of the wood.
[0015] Also provided is a method for coloring and preserving wood
simultaneously.
[0016] Also provided is a method for coloring and preserving wood
comprising the step of impregnating wood with the compositions of
the above embodiments.
[0017] Also provided is a method for coloring and preserving wood
comprising the steps of: [0018] 1) impregnating the wood with a
composition comprising a dispersion comprising one or more
micronized pigments with or without addition of dyes; and [0019] 2)
impregnating the wood with a composition comprising an inorganic or
organic preservative biocide, optionally the biocide is micronized;
[0020] wherein the steps are conducted in either order.
[0021] Also provided is a method for imparting lightfast, uniform
color to wood.
[0022] When wood is treated with the composition of the present
invention, the pigment, and the preservative, if present, are
carried beneath the surface of the wood, imparting long lasting
color to the wood and preserving it from biological
degradation.
[0023] Also provided is a method of impregnating color beneath the
surface of wood to provide for long term application.
[0024] Also provided is a method for imparting color to wood which
improves the outdoor weathering properties of wood.
[0025] Pigment formulations have been used to coat and paint wood.
However, the present invention pertains to the coloring, and,
optionally preserving of wood by impregnation with pigment, and
optionally biocides, giving a preserved product having lightfast,
non-flaking color. Impregnation into wood imparts to the wood
excellent UV resistance, and thus, excellent weathering
characteristics. Impregnation of colorants into wood also
simplifies the coloring process and improves the efficiency and
throughput of coloring and preserving wood compared to traditional
painting and/or staining processes.
[0026] The pigment dispersion comprises micronized inorganic
pigments, such as, for example, iron oxides including red, yellow,
black and brown iron oxides, carbon black, cupric oxide, cuprous
oxide, zinc oxides, titanium oxides and chrome oxides; and/or
micronized organic pigments.
[0027] Also provided is a method for the treatment of wood or wood
product with the compositions of the present invention
BRIEF DESCRIPTION OF THE FIGURES
[0028] FIG. 1 depicts the anatomy of coniferous wood. A: Resin
canal; B: Earlywood tracheids; C: Latewood tracheids; D: Bordered
pits.
[0029] FIG. 2 depicts the border pit structure for coniferous
woods. [0030] RIGHT: Microscopic view of the cross section of a
bordered pit. [0031] LEFT: Torus in top view. The torus is
supported by a net of radial fibril membrane, also called the
margo. The flow of fluids between two tracheids through such a
membrane is restricted by the size of the membrane openings. A: Pit
aperture; B: Torus; C: Margo (microfibrils); D: Pit border.
[0032] FIG. 3 depicts the superior outdoor weathering of wood
treated with tebuconazole and micronized red brown pigment
formulation (3B) versus treatment with tebuconazole alone (3A).
[0033] FIG. 4 depicts the superior outdoor weathering of wood
treated with quaternary ammonium compound and micronized green
pigment formulation (4B) versus treatment with quaternary ammonium
compound alone (4A).
[0034] FIG. 5 demonstrates the effect of QUV test on the wood
samples treated with a preservative alone (dimethyl didecyl
ammonium quat). Delignification and graying were observed after one
month of QUV weathering.
[0035] FIG. 6 demonstrates the effect of QUV test on the wood
samples treated with a preservative (azole based preservative) plus
a light-brown iron oxide-based pigment formulation. Only slight
color change observed after one month of QUV weathering.
DETAILED DESCRIPTION OF THE INVENTION
[0036] The present invention provides compositions and methods for
coloring, and optionally, preserving wood and wood products. The
present invention also provides compositions and methods for
coloring and preserving wood products simultaneously. The
composition comprises a pigment dispersion, and optionally an
organic or inorganic biocide/wood preservative. In some embodiments
of the present invention, the pigments are red iron oxide, yellow
iron oxide, black iron oxide, brown iron oxide, zinc oxide,
titanium oxide, cuprous and cupric oxide, or carbon black. In
additional embodiments, the composition additionally comprises
metal compounds or metal complexes as a preservative, preferably
copper compounds or copper complexes including copper carbonate,
copper hydroxide, oxine copper, cuprous oxide and cupric oxide,
optionally in a micronized form. It should be noted that pigment
compounds may also have biocidal ability as well. In another
embodiment, the preservative composition additionally comprises one
or more organic or metal free biocides, preferably quaternary
ammonium compounds, particularly didecyldimethylammonium chloride,
didecyldimethylammonium carbonate/bicarbonate,
alkyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium
carbonate/bicarbonate, didodecyldimethylammonium chloride,
didodecyldimethylammonium carbonate/bicarbonate,
didodecyldimethylammonium propionate,
N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate; imidazoles
or triazoles, for example, tebuconazole, cyproconazole,
propiconazole, hexaconazole,
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole;
cis-trans-3-chloro-4-[4-methyl-(2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxo-
lan-2-yl]phenyl 4-chlorophenyl ether;
(RS)-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-(trimethylsilyl)propa-
n-2-ol;
2-(2,4-difluorophenyl)-(1H-1,2,4-triazole-1-yl)-3-trimethylsilyl-2-
-propanol; pyrethroids, such as, for example, bifenthrin,
permethrin, cypermethrin; isothiazolone compounds, particularly
4,5-Dichloro-2-n-octyl-3(2H)-isothiazolone (RH-287),
methylisothiazolinone, chloromethylisothiazolinone,
1,2-benzisothiazolin-3- one, 2-octyl-3-isothiazolone; Amine oxides,
particularly Barlox 10, Barlox 12, Barlox 14 and Barlox 16;
imidachloprid; chlorpyrifos; cyfluthrin; fipronil, chlorothalonil
or combinations of the foregoing.
[0037] The present invention pertains to the use of pigment
dispersions to color wood. The present invention also pertains to
the use of pigment dispersions, in combination with organic and/or
inorganic biocides, to color and preserve wood. The difference
between pigments and dyes is generally understood by one of skill
in the art. Pigments are generally more lightfast and have a
greater resistance to UV degradation than dyes. Another difference
is that pigments generally have little or no solubility in the
medium in which they are applied. Thus, if the composition of the
present invention is applied as an aqueous dispersion, the pigment
in the composition is generally one which has little or no
solubility in water. The present invention is primarily directed
toward applications which include the use of pigments in an aqueous
carrier. However, pigment dispersions in other carriers, such as
polar or nonpolar organic carriers, including oil carriers, are
within the ambit of the invention. Non-limiting examples of
non-aqueous carriers which can be used are oil carriers such as,
for example, mineral oil, linseed oil, soybean oil, AWPA p-9 oil,
and other known in the art. In general, the term "pigment" as used
herein refers to a wood coloring compound which, when applied in a
carrier, has a solubility of less than 5g per 100 grams carrier in
the chosen carrier, and preferably less than 1.0 g, 0.5 g, 0.1 g or
0.01 g per 100 grams of carrier (at 25.degree. C.). Furthermore,
the coloring compound also should have a water solubility of less
than 5 g per 100 grams of water at 25.degree. C., and preferably
less than 1.0, 0.5, 0.1 or 0.01 g per 100 g of water.
[0038] The pigments which can be used in the compositions of the
present invention include inorganic and organic pigments. Inorganic
pigments include metal compounds of metals such as iron, zinc,
titanium, lead, chromium, copper, cadmium, calcium, zirconium,
cobalt, magnesium, aluminum, nickel, and other transition metals.
Carbon black is also an inorganic pigment, which can be used in the
present invention.
[0039] Some non-limiting examples of suitable inorganic pigments
include: iron oxides, including red iron oxides, yellow iron
oxides, black iron oxides and brown iron oxides; carbon black, iron
hydroxide, graphite, black micaceous iron oxide aluminum flake
pigments, pearlescent pigments, calcium carbonate, calcium
phosphate, calcium oxide, calcium hydroxide, bismuth oxide, bismuth
hydroxide, bismuth carbonate, copper carbonate, copper hydroxide,
basic copper carbonate, cupric oxide, cuprous oxide, silicon oxide,
zinc carbonate, barium carbonate, barium hydroxide, strontium
carbonate, zinc oxide, zinc phosphate, zinc chromate, barium
chromate, chrome oxide, titanium dioxide, zinc sulfide and antimony
oxide, lead chrome, and cadmium pigments.
[0040] Preferred inorganic pigments are carbon black; graphite;
iron oxides, including yellow, red, black and brown iron oxides;
zinc oxide; titanium oxide and aluminum-based pigments, such as,
for example Al.sub.2O.sub.3 and Al(OH).sub.3.
[0041] Non-limiting examples of organic pigments include Monoazo
(arylide) pigments such as PY3, PY65, PY73, PY74, PY97 and PY98;
Disazo (diarylide); Disazo condensation; Benzimidazolone; Beta
Naphthol; Naphthol; metal-organic complexes; Isoindoline and
Isoindolinone; Quinacridone; perylene; perinone; anthraquinone;
diketo-pyrrolo pyrrole; dioxazine; triacrylcarbonium; the
phthalocyanine pigments, such as cobalt phthalocyanine, copper
phthalocyanine, copper semichloro- or monochlorophthalocyanine,
copper phthalocyanine, metal-free phthalocyanine, copper
polychlorophthalocyanine, phthalocyanine blue, etc.; organic azo
compounds; organic nitro compounds; polycyclic compounds, such as
phthalocyanine pigments, quinacridone pigments, perylene and
perinone pigments; diketopyrrolo-pyrrole(DPP) pigments; thioindigo
pigments; dioxazine pigments; quinophthalone pigments;
triacrylcarbonium pigments, and Diaryl pyrrolopyroles, such as
PR254.
[0042] Non-limiting examples of organic pigments which can be used
in the present invention, grouped according to the color they
produce (e.g. blues, blacks, greens, yellow, reds and browns),
based on their color index include: Pigment Yellows (PY) 1, 11, 3,
12, 13, 14, 17, 81, 83, 65, 73, 74, 75, 97, 111, 120, 151, 154,
175, 181, 194, 93, 94, 95, 128, 166, 129, 153, 109, 110, 173, 139,
185, 138, 108, 24; Pigment Oranges (PO) 5, 36, 60, 62, 65, 68, 61,
38, 69, 31, 13, 34, 43, 51, 71, 73; Pigment Reds (PR) 3, 4, 171,
175, 176, 185, 208, 2, 5, 12, 23, 112, 146, 170, 48, 57, 60, 68,
144, 166, 214, 220, 221, 242, 122, 192, 202, 207, 209, 123, 149,
178, 179, 190, 224, 177, 168, 216, 226, 254, 255, 264, 270, 272;
Pigment Violets (PV) 32, 19, 29, 23, 37; Pigment Browns 25, 23;
Pigment Blacks 1, 31, 32, 20; Pigment Blues (PB)15, 15:1, 15:2,
15:3, 15:4, 15:6, 16, 60; and Pigment Greens (PG) 7, 36.
[0043] It is preferred that the dispersion particle size
distributions (or emulsion droplet size distribution, if
applicable) contain particles (or droplets) of micronized size. The
term "micronized" as used herein means a particle size in the range
of 0.001 to 25 microns.
[0044] It should be understood that "micronized" does not refer
only to particles which have been produced by the finely dividing,
such as by mechanical grinding through media mill, of materials
which are in bulk or other form. Micronized particles can also be
formed by other mechanical, chemical or physical methods, such as,
for example, pulverization process, formation in solution or in
situ, with or without a seeding agent, grinding or impinging jet.
The term "particle size" refers to the largest axis of the
particle. In the case of a generally spherical particle, the
largest axis is the diameter.
[0045] The formulations of micronized inorganic and/or organic
pigments can be obtained by grinding the pigments, optionally
wetted or present as a dispersion, to the desired particle size
using a grinding mill. Other fine particle dividing methods known
in the art can also be used, such as high speed, high shear mixing
or agitation. The resulting particulate additive can be mixed with
an aqueous liquid carrier to form a solution of dispersed additive
particles.
[0046] Optionally, the solution can comprise a thickener, such as,
for example, a cellulose derivative, as is known in the art and/or
resin binder, such as polyacrylic, polyurethane, and other known in
the art.
[0047] The particles are preferably dispersed and stabilized in the
presence of dispersant(s). Dispersants function in micronized
particle systems by 1) replacing the air around the particle
surface and thus wetting the particle; 2) breaking down and/or
preventing formation of particle agglomerates; and 3) stabilizing
ground/reduced particles and preventing flocculation during
storage. Dispersants can be divided into classes, two of which are
polymeric dispersants and conventional low molecular surfactant
type of dispersants. Polymeric dispersants generally possess a
structure with pigment-affinic groups and a polymer chain and
stabilizes the pigment particles through steric hindrance, while
surfactant type dispersants generally possesses a hydrophilic group
and a hydrophobic group and it stabilizes pigment particles through
electrostatic mechanism.
[0048] Pigment stabilization can be particularly important when
using micronized particles in wood treating processes. It not only
requires a stabilized particle during storage, but also requires
that particles maintain stability during repetitive treatments in a
commercial treating plant. During repetitive treating processes, pH
change, wood extractives, wood sugars and contaminants from wood
surface and dirt from air can all affect the function of
dispersants and hence the dispersion particle stability. Many
surfactant-type low molecular weight dispersants can provide
particles with short-term stability; in addition, surfactant-type
low molecular weight dispersants are more sensitive to treatment
environmental variables, such as the wood extractives, wood sugars,
water quality, and degree of shear experienced during treatment. As
a result, surfactant type dispersants are generally not preferred
for the current application in preparing pigment dispersions. The
particles can become unstable during long-term storage and during
treating process and result in agglomeration and aggregation into
large particles. Such agglomerates can impede treatment and leave a
sludge on the surface of treated wood.
[0049] We have surprisingly found that polymeric dispersants can
not only provide long-term stability of pigment dispersion
particles, but also impart a high degree of stability during
repetitive treatment processes. Generally, the weight average
molecular weight of the polymeric dispersants varies from a few
thousand to 100,000 or even more.
[0050] Non-limiting examples of polymeric dispersant classes which
can be used in the compositions of the present invention include
acrylic copolymers, aqueous solution of copolymers with pigment
affinity groups, polycarboxylate ether, modified polyacrylate or
modified polyacrylate with groups of high pigment affinity, acrylic
polymer emulsions, modified acrylic polymers, poly carboxylic acid
polymers and their salts, modified poly carboxylic acid polymers
and their salts, fatty acid modified polyester, aliphatic polyether
or modified aliphatic polyether, solution of polycarboxylate ether,
phosphate esters, phosphate ester modified polymers, polyglycol
ethers or modified polyglycol ethers, polyetherphosphate, modified
maleic anhydride/styrene copolymer, sodium polyacrylate, sodium
polymethacrylate, lignin, modified lignin and the like; modified
polyether or polyester with pigment affinic groups; fatty acid
derivatives; urethane copolymer or modified urethane copolymer,
polyetherphosphate, modified maleic anhydride/styrene copolymer,
modified polycarboxylic acid or its derivatives, acrylic
acid/maleic acid copolymer, polyvinyl pyrrolidone or modified
polyvinyl pyrrolidone, sulfonates or sulfonate derivatives,
polymeric alkoxylate or its derivatives, or modified lignin and the
like. If desired, a stabilizer as is known in the art can be used.
Other dispersants can be found in 2004 McCutcheon's Functional
Materials (North American Edition).
[0051] We have found that polymeric dispersants, especially
modified polycarboxylate ether, modified poly carboxylic acid
polymers and their salts, solutions of polycarboxylate ethers;
modified polyether or polyester with pigment affinic groups,
perform well with inorganic pigment compounds, particularly iron
oxides, in providing wetting, dispersing, storage stabilization and
stability during treatment process. We have also found that
polymeric dispersants, particularly modified maleic
anhydride/styrene copolymer or acrylic acid/maleic acid copolymer,
perform well with organic pigments in providing wetting,
dispersing, storage stabilization and stability during repetitive
treating process.
[0052] For inorganic pigments, such as iron oxides, the level of
dispersant is preferably in the range of from about 0.1 to 180% of
the weight of the pigment compounds, and in other embodiments, in
the range of 1 to 80%, 5 to 60%, and 10 to 30%. For organic
pigments, the level of dispersant is preferably in the range of
from about 1 to 200% of the weight of the pigment compounds, and in
other embodiments in the range of 5 to 100%, 10 to 80%, and 30 to
70%.
[0053] If desired, a wetting agent can be used in the preparation
of the compositions of the present invention. The level of wetting
agent is preferably in the range of from about 0.1 to 50% of the
weight of the pigment, and in other embodiments in the range of 0.5
to 10%, and 0.5 to 5%.
[0054] The composition of the present invention can be a
concentrate or a preparation which is ready to apply to wood. In
general, the total pigment concentrate is in the range of from 1 wt
% to 80 wt %, based on weight of the composition, and preferably in
the range of from 5 to 70 wt %, and more preferably in the range of
from 30 to 65 wt %.
[0055] In the composition of the present invention, it is
preferable that the pigment dispersion be present in the treating
liquid applied to wood in amounts in the range of from 0.005 to 50
wt % of the solution, with a preferred range of 0.01 to 20%, and a
more preferred range of 0.05 to 10%, and an even more preferred
range of 0.1 to 1.0%.
[0056] A preferred method of preparing the pigment particles is by
grinding. An exemplary method involves the formation of a slurry
comprising a dispersant, a carrier, and a powdered pigment having a
particle size in the range of from 1 micron to 500 microns, and
optionally, a defoamer. The slurry is transferred to a grinding
mill which is prefilled with a grinding media having a size in the
range of from 0.05 mm to 5 mm, and preferably between 0.1 and 1 mm.
The media can be one or more of many commercially available types,
including but not limited to steel shots, carbon steel shots,
stannous steel shots, chrome steel shots, ceramic (for example,
alumina-containing); zirconium-based, such as zirconia, zirconium
silicate, zirconium oxide stabilized zirconia such as
yttrium-stabilized zirconia and ceria-stabilized zirconia;
stabilized magnesium oxide; stabilized aluminum oxide, etc. The
medium preferably occupies 50% to 99% of the grinding chamber
volume, with 75 to 95% preferred, and 80 to 90% more preferred. The
bulk density of the grinding media is preferably in the range of
from 0.5 kg/l to 10 kg/l, and more preferably in the range of from
2 to 5 kg/l. Agitation speed, which can vary with the size of the
grinder, is generally in the range of from 1 to 5000 rpm, but can
be higher or lower. Lab and commercial grinders generally run at
different speeds. A set up which involves a transfer pump which
repeatedly cycles the slurry between the mill and a storage tank
during grinding is convenient. The transfer pump speed varies from
1 to 500 rpm, and the speeds for lab and commercial grinders can be
different. During grinding, defoamer can be added if foaming is
observed. During grinding, particle size distribution can be
analyzed, and once particle size is within the desired
specification, grinding is stopped.
[0057] In the compositions of the present invention, in some
embodiments, it preferred that at least 98% of the particles (by
weight) have a diameter less than 10 microns, less than 5 microns
or less than 1 micron.
[0058] The penetration of the pigment dispersion formulation into
the cellular structure of wood or other cellulose-based material is
dependent upon particle size considerations. If the
inorganic/organic pigments used in formulating the dispersion
formulation disclosed herein have a particle size in excess of 25
microns, the particles may be filtered by the surface of the wood
and thus may not be uniformly distributed within the cell and cell
wall.
[0059] In addition to the pigment dispersions, the present
invention may comprise an inorganic and/or organic biocide
component. This component may be micronized, emulsified, or present
in solution. The above particle size considerations apply to the
total particulate content, whether the particles are pigments or
other particulate composition components. Although it is desirable
to prepare separate concentrates of micronized pigments and
micronized biocides and combine them to make treating compositions
in the treating plant, a blended concentrate of micronized pigments
and, optionally, micronized biocides and treating compositions can
be obtained by direct dilution.
[0060] Non-limiting examples of inorganic biocides include
materials such as metal complexes and metal compounds, as well as
alkaline metal complexes and other metal complexes. Suitable metals
include copper, arsenic, zinc, silver, cadmium, nickel, bismuth,
lead and chromium, with copper being preferred. Suitable metal
compounds and complexes can be obtained as concentrates, such as
copper oxides, copper carbonate, copper omadine, copper
8-hydroxyquinolate (oxine copper).
[0061] The metal compounds, such as copper compounds, can also be
in micronized particulate form when used with pigment dispersion.
The preparation of the micronized metal compounds and the particle
size range and distribution are similar to those of micronized
pigments.
[0062] In addition to or instead of metal compounds and/or metal
complexes, the present invention can also comprise organic biocidal
compounds.
[0063] Some non-limiting examples of organic biocides are listed as
follows:
Aliphatic Nitrogen Fungicides
[0064] butylamine; cymoxanil; dodicin; dodine; guazatine;
iminoctadine Amide Fungicides [0065] carpropamid;
chloraniformethan; cyazofamid; cyflufenamid; diclocymet; ethaboxam;
fenoxanil; flumetover; furametpyr; prochloraz; quinazamid;
silthiofam; triforine benalaxyl; benalaxyl-M; furalaxyl; metalaxyl;
metalaxyl-M; pefurazoate; benzohydroxamic acid; tioxymid;
trichlamide; zarilamid; zoxamide cyclafuramid; furmecyclox
dichlofluanid; tolylfluanid benthiavalicarb; iprovalicarb
benalaxyl; benalaxyl-M;boscalid; carboxin; fenhexamid; metalaxyl;
metalaxyl-M metsulfovax; ofurace; oxadixyl;
oxycarboxin;pyracarbolid; thifluzamide; tiadinil benodanil;
flutolanil; mebenil; mepronil; salicylanilide; tecloftalam
fenfuram; furalaxyl; furcarbanil; methfuroxam flusulfamide
Antibiotic Fungicides [0066] aureofungin; blasticidin-S;
cycloheximide; griseofulvin; kasugamycin;natamycin; polyoxins;
polyoxorim; streptomycin; validamycin azoxystrobin dimoxystrobin
fluoxastrobin kresoxim-methyl metominostrobin orysastrobin
picoxystrobin pyraclostrobin trifloxystrobin Aromatic Fungicides
[0067] biphenyl chlorodinitronaphthalene chloroneb chlorothalonil
cresol dicloran hexachlorobenzene pentachlorophenol quintozene
sodium pentachlorophenoxide tecnazene Benzimidazole Fungicides
[0068] benomyl carbendazim chlorfenazole cypendazole debacarb
fuberidazole mecarbinzid rabenzazole thiabendazole Benzimidazole
Precursor Fungicides [0069] furophanate thiophanate
thiophanate-methyl Benzothiazole Fungicides [0070] bentaluron
chlobenthiazone TCMTB Bridged Diphenyl Fungicides [0071] bithionol
dichlorophen diphenylamine Carbamate Fungicides [0072]
benthiavalicarb furophanate iprovalicarb propamocarb thiophanate
thiophanate-methyl benomyl carbendazim cypendazole debacarb
mecarbinzid diethofencarb Conazole Fungicides [0073] climbazole
clotrimazole imazalil oxpoconazole prochloraz triflumizole
azaconazole bromuconazole cyproconazole diclobutrazol
difenoconazole diniconazole diniconazole-M epoxiconazole
etaconazole fenbuconazole fluquinconazole flusilazole flutriafol
furconazole furconazole-cis hexaconazole imibenconazole ipconazole
metconazole myclobutanil penconazole propiconazole prothioconazole
quinconazole simeconazole tebuconazole tetraconazole triadimefon
triadimenol triticonazole uniconazole uniconazole-P Dicarboximide
Fungicides [0074] famoxadone fluoroimide chlozolinate dichlozoline
iprodione isovaledione myclozolin procymidone vinclozolin captafol
captan ditalimfos folpet thiochlorfenphim Dinitrophenol Fungicides
[0075] binapacryl dinobuton dinocap dinocap-4 dinocap-6 dinocton
dinopenton dinosulfon dinoterbon DNOC Dithiocarbamate Fungicides
[0076] azithiram carbamorph cufraneb cuprobam disulfiram ferbam
metam nabam tecoram thiram ziram dazomet etem milneb mancopper
mancozeb maneb metiram polycarbamate propineb zineb Imidazole
Fungicides [0077] cyazofamid fenamidone fenapanil glyodin iprodione
isovaledione pefurazoate triazoxide Morpholine Fungicides [0078]
aldimorph benzamorf carbamorph dimethomorph dodemorph fenpropimorph
flumorph tridemorph Organophosphorus Fungicides [0079] ampropylfos
ditalimfos edifenphos fosetyl hexylthiofos iprobenfos phosdiphen
pyrazophos tolclofos-methyl triamiphos Oxathiin Fungicides [0080]
carboxin oxycarboxin Oxazole Fungicides [0081] chlozolinate
dichlozoline drazoxolon famoxadone hymexazol metazoxolon myclozolin
oxadixyl vinclozolin Pyridine Fungicides [0082] boscalid buthiobate
dipyrithione fluazinam pyridinitril pyrifenox pyroxychlor pyroxyfur
Pyrimidine Fungicides [0083] bupirimate cyprodinil diflumetorim
dimethirimol ethirimol fenarimol ferimzone mepanipyrim nuarimol
pyrimethanil triarimol Pyrrole Fungicides [0084] fenpiclonil
fludioxonil fluoroimide Quinoline Fungicides [0085] ethoxyquin
halacrinate 8-hydroxyquinoline sulfate quinacetol quinoxyfen
Quinone Fungicides [0086] benquinox chloranil dichlone dithianon
Quinoxaline Fungicides [0087] chinomethionat chlorquinox thioquinox
Thiazole Fungicides [0088] ethaboxam etridiazole metsulfovax
octhilinone thiabendazole thiadifluor thifluzamide Thiocarbamate
Fungicides [0089] methasulfocarb prothiocarb Thiophene Fungicides
[0090] ethaboxam silthiofam Triazine Fungicides [0091] anilazine
Triazole Fungicides [0092] bitertanol fluotrimazole triazbutil Urea
Fungicides [0093] bentaluron pencycuron quinazamid Other Fungicides
[0094] acibenzolar acypetacs allyl alcohol benzalkonium chloride
benzamacril bethoxazin carvone chloropicrin DBCP dehydroacetic acid
diclomezine diethyl pyrocarbonate fenaminosulf fenitropan
fenpropidin formaldehyde furfural hexachlorobutadiene iodomethane
isoprothiolane methyl bromide methyl isothiocyanate metrafenone
nitrostyrene nitrothal-isopropyl OCH 2 phenylphenol phthalide
piperalin probenazole proquinazid pyroquilon sodium
orthophenylphenoxide spiroxamine sultropen thicyofen tricyclazole,
methyl isothiocyanate
[0095] Preferred insecticides which can be mixed micronized metal
formulations are:
Antibiotic Insecticides
[0096] allosamidin thuringiensin spinosad abamectin doramectin
emamectin eprinomectin ivermectin selamectin milbemectin milbemycin
oxime moxidectin Botanical Insecticides [0097] anabasine
azadirachtin d-limonene nicotine pyrethrins cinerins cinerin I
cinerin II jasmolin I jasmolin II pyrethrin I pyrethrin II quassia
rotenone ryania sabadilla Carbamate Insecticides [0098] bendiocarb
carbaryl benfuracarb carbofuran carbosulfan decarbofuran
furathiocarb dimetan dimetilan hyquincarb pirimicarb alanycarb
aldicarb aldoxycarb butocarboxim butoxycarboxim methomyl
nitrilacarb oxamyl tazimcarb thiocarboxime thiodicarb thiofanox
allyxycarb aminocarb bufencarb butacarb carbanolate cloethocarb
dicresyl dioxacarb EMPC ethiofencarb fenethacarb fenobucarb
isoprocarb methiocarb metolcarb mexacarbate promacyl promecarb
propoxur trimethacarb XMC xylylcarb Dinitrophenol Insecticides
[0099] dinex dinoprop dinosam DNOC cryolite sodium
hexafluorosilicate sulfluramid Formamidine Insecticides [0100]
amitraz chlordimeform formetanate formparanate Fumigant
Insecticides [0101] acrylonitrile carbon disulfide carbon
tetrachloride chloroform chloropicrin para-dichlorobenzene
1,2-dichloropropane ethyl formate ethylene dibromide ethylene
dichloride ethylene oxide hydrogen cyanide iodomethane methyl
bromide methylchloroform methylene chloride naphthalene phosphine
sulfuryl fluoride tetrachloroethane Insect Growth Regulators [0102]
bistrifluron buprofezin chlorfluazuron cyromazine diflubenzuron
flucycloxuron flufenoxuron hexaflumuron lufenuron novaluron
noviflumuron penfluron teflubenzuron triflumuron epofenonane
fenoxycarb hydroprene kinoprene methoprene pyriproxyfen triprene
juvenile hormone I juvenile hormone II juvenile hormone III
chromafenozide halofenozide methoxyfenozide tebufenozide
.alpha.-ecdysone ecdysterone diofenolan precocene I precocene II
precocene III dicyclanil Nereistoxin Analogue Insecticides [0103]
bensultap cartap thiocyclam thiosultap flonicamid clothianidin
dinotefuran imidacloprid thiamethoxam nitenpyram nithiazine
acetamiprid imidacloprid nitenpyram thiacloprid Organochlorine
Insecticides [0104] bromo-DDT camphechlor DDT pp'-DDT ethyl-DDD HCH
gamma-HCH lindane methoxychlor pentachlorophenol TDE aldrin
bromocyclen chlorbicyclen chlordane chlordecone dieldrin dilor
endosulfan endrin HEOD heptachlor HHDN isobenzan isodrin kelevan
mirex Organophosphorus Insecticides [0105] bromfenvinfos
chlorfenvinphos crotoxyphos dichlorvos dicrotophos dimethylvinphos
fospirate heptenophos methocrotophos mevinphos monocrotophos naled
naftalofos phosphamidon propaphos schradan TEPP tetrachlorvinphos
dioxabenzofos fosmethilan phenthoate acethion amiton cadusafos
chlorethoxyfos chlormephos demephion demephion-O demephion-S
demeton demeton-O demeton-S demeton-methyl demeton-O-methyl
demeton-S-methyl demeton-S-methylsulphon disulfoton ethion
ethoprophos IPSP isothioate malathion methacrifos oxydemeton-methyl
oxydeprofos oxydisulfoton phorate sulfotep terbufos thiometon
amidithion cyanthoate dimethoate ethoate-methyl formothion mecarbam
omethoate prothoate sophamide vamidothion chlorphoxim phoxim
phoxim-methyl azamethiphos coumaphos coumithoate dioxathion
endothion menazon morphothion phosalone pyraclofos pyridaphenthion
quinothion dithicrofos thicrofos azinphos-ethyl azinphos-methyl
dialifos phosmet isoxathion zolaprofos chlorprazophos pyrazophos
chlorpyrifos chlorpyrifos-methyl butathiofos diazinon etrimfos
lirimfos pirimiphos-ethyl pirimiphos-methyl primidophos pyrimitate
tebupirimfos quinalphos quinalphos-methyl athidathion lythidathion
methidathion prothidathion isazofos triazophos azothoate bromophos
bromophos-ethyl carbophenothion chlorthiophos cyanophos cythioate
dicapthon dichlofenthion etaphos famphur fenchlorphos fenitrothion
fensulfothion fenthion fenthion-ethyl heterophos jodfenphos
mesulfenfos parathion parathion-methyl phenkapton phosnichlor
profenofos prothiofos sulprofos temephos trichlormetaphos-3
trifenofos butonate trichlorfon mecarphon fonofos trichloronat
cyanofenphos EPN leptophos crufomate fenamiphos fosthietan
mephosfolan phosfolan pirimetaphos acephate isocarbophos isofenphos
methamidophos propetamphos dimefox mazidox mipafox Oxadiazine
Insecticides [0106] indoxacarb Phthalimide Insecticides [0107]
dialifos phosmet tetramethrin Pyrazole Insecticides [0108]
acetoprole ethiprole fipronil tebufenpyrad tolfenpyrad vaniliprole
Pyrethroid Insecticides [0109] acrinathrin allethrin bioallethrin
barthrin bifenthrin bioethanomethrin cyclethrin cycloprothrin
cyfluthrin beta-cyfluthrin cyhalothrin gamma-cyhalothrin
lambda-cyhalothrin cypermethrin alpha-cypermethrin
beta-cypermethrin theta-cypermethrin zeta-cypermethrin cyphenothrin
deltamethrin dimefluthrin dimethrin empenthrin fenfluthrin
fenpirithrin fenpropathrin fenvalerate esfenvalerate flucythrinate
fluvalinate tau-fluvalinate furethrin imiprothrin metofluthrin
permethrin biopermethrin transpermethrin phenothrin prallethrin
profluthrin pyresmethrin resmethrin bioresmethrin cismethrin
tefluthrin terallethrin tetramethrin tralomethrin transfluthrin
etofenprox flufenprox halfenprox protrifenbute silafluofen
Pyrimidinamine Insecticides [0110] flufenerim pyrimidifen Pyrrole
Insecticides [0111] chlorfenapyr Tetronic Acid Insecticides [0112]
spiromesifen Thiourea Insecticides [0113] diafenthiuron Urea
Insecticides [0114] flucofuron sulcofuron Other Insecticides [0115]
closantel crotamiton EXD fenazaflor fenoxacrim hydramethylnon
isoprothiolane malonoben metoxadiazone nifluridide pyridaben
pyridalyl rafoxanide triarathene triazamate
[0116] Preferred bactericides include: [0117] bronopol cresol
dichlorophen dipyrithione dodicin fenaminosulf formaldehyde
hydrargaphen 8-hydroxyquinoline sulfate kasugamycin nitrapyrin
octhilinone oxolinic acid oxytetracycline probenazole streptomycin
tecloftalam thiomersal
[0118] Preferred biocides include: azole compounds, such as
tebuconazole; cyproconazole; propiconazole; hexaconazole,
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole;
cis-trans-3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxol-
an-2-yl]phenyl 4-chlorophenyl ether;
(RS)-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-(trimethylsilyl)propa-
n-2-ol;
2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazole-1-yl)-3-trimethylsilyl-
-2-propanol; isothiazolone compounds, such as
methylisothiazolinone; chloromethylisothiazolinone;
4,5-Dichloro-2-n-octyl-3(2H)-isothiazolone;
1,2-benzisothiazolin-3-one; 2-octyl-3-isothiazolone; imidachloprid;
fipronil; cyfluthrin; bifenthrin; permethrin; cypermethrin; and
chlorpyrifos; iodopropynyl butylcarbamate (IPBC); chlorothalonil;
2-(thiocyanatomethylthio) benzothiazole; alkoxylated diamines and
carbendazim.
[0119] Organic biocides also include quaternary ammonium compounds
disclosed in the present invention have the following structures:
##STR1## where R1, R2, R3, and R4 are independently selected from
alkyl or aryl groups and X.sup.- selected from chloride, bromide,
iodide, carbonate, bicarbonate, borate, carboxylate, hydroxide,
sulfate, acetate, laurate, or any other anionic group.
[0120] Preferred quaternary ammonium compounds include
didecyldimethylammonium chloride; didecyldimethylammonium
carbonate/bicarbonate; alkyldimethylbenzylammonium chloride;
alkyldimethylbenzylammonium carbonate/bicarbonate;
didodecyldimethylammonium chloride; didodecyldimethylammonium
carbonate/bicarbonate; didodecyldimethylammonium propionate;
N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate.
[0121] Without desiring to be bound by theory, penetration of the
micronized dispersion formulation into wood takes place because
particles migrate into or are taken up by tracheids in the wood.
FIG. 1 shows the physiological structure of wood. As shown in FIG.
1, the primary entry and movement of fluids through wood tissue
occurs primarily through the tracheids and border pits. Fluids are
transferred between wood cells by means of border pits, which are
generally smaller in diameter than the tracheids. When wood is
treated with micronized pigment dispersion, if the particle size of
the pigment is less than the diameter of the pit openings, a
complete penetration and a uniform distribution of micronized
preservative in wood is expected. Wood tracheids generally have
diameters of around 30 microns, and good penetration can be
achieved by the use of particles having long axis dimensions
("particle size" which are less than the tracheid diameters of the
wood or wood product to be treated.
[0122] Studies by Mercury-Porosimetry technique indicated that the
overall diameter of the border pit chambers typically varies from a
several microns up to thirty microns while, the diameter of the pit
openings (via the microfibrils) typically varies from several
hundredths of a micron to several microns. FIG. 2 depicts the
border pit structure for coniferous woods. Thus, in order to
maximize penetration and uniformity of distribution of the
particulate composition, the particle size should be such that it
can travel through the pit openings.
[0123] The size of the particles used in the dispersion formulation
disclosed herein can be micronized, i.e., with a long axis
dimension between 0.001-25 microns. In another embodiment, the
particle size is between 0.001-10 microns. In another embodiment,
the particle size is between 0.01-5 microns. In yet another
embodiment, the particle size is between 0.01 to 2 microns. If
superior uniformity of penetration is desired, particle size of the
additive used in the dispersion formulation disclosed herein should
be between 0.05-1 microns.
[0124] It should be noted that the above does not exclude the
presence of particles outside the stated ranges. However, particles
which are too large can clog the wood, preventing it from taking in
other particles. Thus particle size distributional parameters can
affect the uniformity of particle distribution in the wood, as well
as the leaching properties of treated wood. It is thus preferable
to use particle size distributions which contain relatively few
particle sizes outside the range of 0.001 to 25 microns. It is
preferred that no more than 20 weight percent of the particles have
diameters which are greater than 25 microns. Regardless of the
foregoing recommendations, it is generally preferred that at least
60%, and more preferably, at least 80 wt % of the particles have a
diameter in the range of 0.001 to 25 microns. In more preferred
embodiments, greater than 85, 90, 95 or 99 wt percent particles are
in the range of 0.001 to 25 microns. Depending on the degree of
penetration desired, greater than 5, 10, 20 or 50 wt % of the
particles can be less than 5, 1 or 0.5 microns.
[0125] For increased degree of penetration and uniformity of
distribution, at least 50 wt % of the particles should have
diameters which are less than 10 microns. More preferred are
particle distributions which have at least 80, 90, 95, or 99 wt %
of the particles with sizes of less than 10 microns. In an
additional embodiment, at least 60 wt % of the particles should
have diameters which are less than 1 micron. More preferred are
particle distributions which have at least 80, 90, 95, or 99 wt %
of the particles with sizes of less than 1 micron.
[0126] In order to further improve the weathering properties and
the lightfastness of the pigment treated wood or further improve
the adhesion of pigment particles to wood, a resin binder is often
used in the composition. Examples of resin binders which can be
used include polyurethane, polyester, polyvinyl alcohol, polyamide,
epoxy, acrylic polymers, vinyl polymers (including polymers made
from ethylenically unsaturated monomers such as polybutene),
cellulosic derivatives, oligomers and natural polymers, can be
either added to the pigment dispersion or added to the final
treating composition. Examples of resin binders include: [0127] 1).
Natural resins, such as fatty vegetable oils, mixtures of complex
cyclic or aromatic acids, fish oils, and the like. [0128] 2). Vinyl
based resins, such as polyethylene, polypropylene, polyvinyl
chloride, polyvinyl alcohol, polystyrene, polyalpha methyl styrene,
polyvinyl acetate, polymethyl methacrylate, polyacrylonitrile,
polyvinyl ethyl ether, polyvinylidene fluoride and the like. [0129]
3). Acrylic resins, such as polyacrylic acid, polymethacrylic acid,
polyethyl acrylate, polymethyl methacrylate, polylauryl
methacrylate, poly2-hydroxyethyl acylate, polyglycidal
methaacylate, polyacrylamide, polyhexane diol diacylate,
polytrimethylol propane triacrylate, polycarboxylic acid, and the
like. [0130] 4). Hydrocarbon resins and bituminous binders, such as
petroleum oil-derived hydrocarbon resins, terpene resins, ketone
resins, asphltite, petroleum asphalts, bituminous mastics,
asphaltic hybrids, and the like. [0131] 5). Cellulosic resins, such
as nitrocellulose, cellulose acetate, cellulose acetate butyrate,
ethylcellulose, carboxylmethyl cellulose, methyl cellulose, ethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl
hydroxyethyl cellulose, and the like. [0132] 6). Vegetable oils and
modified vegetable oils, such as castor oil, linseed oil, tung oil,
soya oil, tall oil, safflower oil, fish oil, and the like. [0133]
7). Alkyd resins, such as polyethylene glycol, polyneopentyl
glycol, polyglycerol, polypentaerythritol, polybenzoic acid,
polyabietic acid, polyterephthalic acid, polytrimellitic anhydride,
polyisophthalic acid, polyamide-modified alkyds, and the like.
[0134] 8). Polyester and polyesteramide resins, such as
polyethylene terephthalate. The polyesters can be obtained, as well
known, by polycondensation of dicarboxylic acids with polyols, in
particular diols. The polyesteramides can be obtained in a similar
manner to that for the polyesters, by polycondensation of diacids
with diamines or amino alcohols, and the like. [0135] 9).
Formaldehyde resins, such as phenolic resins including phenolic
novolacs, phenolic resoles, phenolic epoxies, and phenolic modified
rosins, amino resins including urea formaldehyde resins, melamine
formaldehyde resins and hexamethoxymethyl melamine resins, and the
like. [0136] 10). Epoxy resins, such as bisphenol A based epoxy
resins, bisphenol F epoxy resins, polyglycol epoxy resins,
cardanol-based epoxies and brominated epoxies, and the like. [0137]
11). Polyurethanes: The polyurethanes may be chosen from anionic,
cationic, nonionic or amphoteric polyurethanes, acrylic
polyurethanes, polyurethane-polyvinylpyrrolidones,
polyester-polyurethanes, polyether-polyurethanes, polyureas,
polyurea-polyurethanes and mixtures thereof. The polyurethane can
be, for example, an aliphatic, cycloaliphatic or aromatic
polyurethane, polyurea/urethane or polyurea copolymer containing,
alone or as a mixture: one sequence of linear or branched aliphatic
and/or cycloaliphatic and/or aromatic polyester origin, and/or one
sequence of aliphatic and/or cycloaliphatic and/or aromatic
polyether origin. The polyurethanes can also be obtained from
branched or unbranched polyesters, or from alkyds containing labile
hydrogens which are modified by reaction with a diisocyanate and a
difunctional (for example dihydro, diamino or hydroxyamino) organic
compound, in addition containing either a carboxylic acid or
carboxylate group, or a sulphonic acid or sulphonate group, or
alternatively a tertiary amine group or a quaternary ammonium
group, and the like. [0138] 12). Silicone Resins: the silicone
compounds, in emulsion, are preferably polyorganosiloxanes, which
can be provided in the form of oils, in particular, volatile or
nonvolatile silicone oil, of gums, of resins, of pasty products or
of waxes, or their mixtures. The silicone gums, waxes and resins
can be mixed with silicone oils in which they may be dissolved, the
mixture being in the form of an oil-in-water emulsion. [0139] 13).
Silicate resins, such as alkali silicate binders, alkyl silicate
binders, cementitious binders and zinc rich silicate binders, and
the like.
[0140] In the composition of the present invention, the ratio of
the resin content to the pigment solid content in the treating
composition ranges from about 0.001:1 to about 1000:1, and
preferably ranges from about 0.01:1 to about 10:1, and more
preferably range from 0.05:1 to about 1:1.
[0141] In the present invention dyes can optionally be added to the
pigment compositions or preservative composition or treating
compositions to obtain the desirable color and enhance the color
richness of the treated wood. Dyes can be basic dyes (or cationic
dyes), acid dyes, direct dyes, azoic dyes, sulfur dyes, vat dyes,
and reactive dyes. Preferred dyes are basic dyes.
[0142] Non-limiting examples of basic dyes are: derivatives of
diphenylmethane; triphenylmethane or acridine; thiazine, oxazine,
or azine dyes; xanthene basic dyes, basic dyes containing azo
groups, and basic dyes containing a pendant cation, a delocalized
charge, or a heterocylic ring which contains a quaternary nitrogen
atom; 2-(((4-Methoxyphenyl)methylhydrazono)
methyl)-1,3,3-trimethyl-3H-indolium methyl sulphate;
2-(2-(4-((2-Chloroethyl)
methylamino)phenyl)vinyl)-1,3,3-trimethyl-3H-indolium chloride;
3,7-Bis(dimethylamino)phenothiazin-5-ium chloride;
7-(Dimethylamino)-6-nitro-3H-phenothiazin-3-ylidene)dimethylammonium
chloride; Methanaminium
N-[4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexadien-1-ylide-
ne]-N-methyl-, chloride;
4-((4-aminophenyl)(4-imino-2,5-cyclohexadien-1-ylidene)methyl)-2-methyl-b-
enzenamine;
4,4'-((4-imino-2,5-cyclohexadien-1-ylidene)methylene)dianiline
monohydrochloride; 1,3-Benzenediamine,
4,4'-(1,3-phenylenebis(azo))bis-, dihydrochloride;
3-Methyl-2-((1-methyl-2-phenyl-1H-indol-3-yl)azo)thiazolium
chloride; (2-((4-((2-Chloro-4-nitrophenyl)azo)phenyl)ethylamino)
ethyl)trimethylammonium methyl sulphate;
2-(((1,3-Dihydro-1,3-dimethyl-2H-benzimidazol-2-ylidene)methyl)azo)-3-met-
hylbenzothiazolium methyl sulphate;
(2-((4-((2-Chloro-4-nitrophenyl)azo)phenyl)ethylamino)ethyl)trimethylammo-
nium;
4-((2-Chlorophenyl)(4-(ethylimino)-3-methylcyclohexa-2,5-dien-1-ylid-
ene)methyl)-N-ethyl-o-toluidine monohydrochloride;
2-(2-(4-((2-Chloroethyl)ethylamino)-o-tolyl)vinyl)-1,3,3-trimethyl-3H-ind-
olium chloride.
[0143] Non-limiting examples of acid dyes are: derivatives of
triphenylmethane, derivatives of xanthene, nitrated aromatic
compounds, acid dyes containing one or more azo groups, pyrazolone
azo dyes, derivatives of anthraquinone dyes, derivatives of
phthalocyanine dyes. Non-limiting examples of direct dyes are:
sulphonated azo compounds and metal complex direct dyes.
[0144] In the composition of the present invention, the ratio of
the dye content to the pigment content in the treating composition
ranges from about 0.001:1 to about 1000:1, and preferably ranges
from about 0.01:1 to about 10:1, and more preferably range from
0.05:1 to about 1:1.
[0145] A wide range of useful colors can be imparted to wood using
the process of the present invention. The color of wood treated
with the preservative solutions described herein can be a variety
of colors, such as grey, blue, green, brown, yellow, orange, black,
red or other shades, depending upon the particular combination of
the pigments, and their concentration. Dramatic improvement on the
weathering properties can be achieved by incorporating the pigments
into preservative systems as shown in FIGS. 3 and 4. The samples in
FIG. 3 were treated with a tebuconazole based wood preservative and
the samples in FIG. 4 with a quaternary ammonium compound-based
wood preservative (dimethyl didecyl ammonium
carbonate/bicarbonate). Specifically, the samples in FIGS. 3A and
4A were treated with the preservatives alone, while the sample in
FIG. 3B was treated with the preservative plus a red-brown iron
oxide-based pigment formulation and 4B with the preservative plus a
iron oxide/carbon black-based green pigment formulation. The
samples were then subjected to outdoor weathering. The samples
treated with preservative alone showed poor weathering
characteristics: delignification, surface graying, darkening, and
mold growth, while the samples treated with preservatives plus
pigments demonstrated excellent photo-resistance and overall color
integrity.
[0146] Laboratory accelerated weathering test (QUV Test: samples
exposed to UV light and water spraying) also confirms that the wood
samples treated with preservative plus pigment formulation
demonstrated great UV photo-resistance. FIGS. 5 and 6 demonstrated
the effect of QUV test on the wood samples treated with a
preservative alone (tebuconazole and bifenthrin) and the
preservative plus a light-brown pigment formulation (iron
oxide-based), respectively. Delignification and graying were
observed on the preservative alone treated sample after one month
QUV weathering, while only slight color change was observed the
sample treated with the preservative plus the pigment after one
month QUV weathering.
[0147] The treating composition may be applied to wood by dipping,
soaking, spraying, brushing, or any other means well known in the
art. In a preferred embodiment, vacuum and/or pressure techniques
are used to impregnate the wood in accord with this invention
including the standard processes, such as the "Empty Cell" process,
the "Modified Full Cell" process and the "Full Cell" process, and
any other vacuum and/or pressure processes which are well known to
those skilled in the art.
[0148] The standard processes are defined as described in AWPA
Standard C1-03 "All Timber Products--Preservative Treatment by
Pressure Processes". In the "Empty Cell" process, prior to the
introduction of preservative, materials are subjected to
atmospheric air pressure (Lowry) or to higher air pressures
(Rueping) of the necessary intensity and duration. In the "Modified
Full Cell", prior to introduction of preservative, materials are
subjected to a vacuum of less than 77 kPa (22 inch Hg) (sea level
equivalent). A final vacuum of not less than 77 kPa (22 inch Hg)
(sea level equivalent) should be used. In the "Full Cell Process",
prior to introduction of preservative or during any period of
condition prior to treatment, materials are subjected to a vacuum
of not less than 77 kPa (22 inch Hg). A final vacuum of not less
than 77 kPa (22 inch Hg) is used.
[0149] The present invention also provides a method for applying
pigments to wood. In one embodiment, the method comprises the steps
of treating wood with a treating fluid comprising a dispersion of
micronized pigment particles according to conventional wood
treatment cycles employing for example, the Full Cell or Empty Cell
process, some combination thereof, or by dip or spray
treatment.
[0150] It is preferable to color and preserve the wood
simultaneously, however it can be desirable to treat and color the
wood in two stages. Without departing from the teachings of this
invention the wood may first be treated with a composition
containing wood preservatives, and then contacted with a
composition containing the pigment dispersion. It is also possible
to apply the coloring agent to the wood initially, followed by the
application of the preservative composition. The application of
each component can be carried out as with the application of a two
component solution.
[0151] The two step application is particularly useful in wood
treatment processes in which the runoff from treatment with one
component is to be collected and reused.
[0152] A variety of cellulosic products such as wood, paper,
textiles, cotton and the like can be colored and preserved in
accordance with this invention including hard and/or soft woods. In
general, wood may thus be simultaneously colored and preserved.
[0153] Wood colored and preserved according to the method of this
invention resists weathering and has many uses in the construction
industry. Patio and pool decks, wood siding and beams, fence posts,
garden ties and poles for outdoor or indoor use are just a few of
the possible products which may incorporate wood treated according
to the method described herein.
[0154] The following examples will serve to further illustrate the
invention. Examples 1 through 10 demonstrate the preparation of
pigment dispersion. Examples 15 through 22 demonstrate the
preparation of the wood preservative treating compositions with and
without the presence of pigment dispersions.
EXAMPLE 1
[0155] 1500 grams of red iron oxide, 500 g yellow iron oxide and 56
g carbon black were added to a container containing 1594.0 g of
water and 350.0 g of a commercially available solution of
polycarboxylate ether dispersant. The mixture was mechanically
stirred for about 20 minutes and then added to a grinding mill. The
sample was ground for about 2.0 hours and a stable dispersion was
obtained. The particle size of the dispersed product was analyzed
by Horiba LA-910 Particle Size Distribution Analyzer (PSDA). The
average particle size was 0.21 microns with a distribution range of
0.04 um to 1.0 um.
EXAMPLE 2
[0156] 800 grams of red iron oxide, 200 g yellow iron oxide and 25
g carbon black were added to a container containing 795.0 g of
water and 180 g of a modified poly carboxylic acid polymers
dispersant. The mixture was mechanically stirred for about 20
minutes and then added to a grinding mill. The sample was ground
for about 1.1 hours and a stable dispersion was obtained. The
particle size of the dispersed product was analyzed by Horiba
LA-910 Particle Size Distribution Analyzer (PSDA). The average
particle size was 0.18 microns with a distribution range of 0.04 um
to 1.5 um.
EXAMPLE 3
[0157] 750 grams of red iron oxide, 250 g yellow iron oxide and 50
g black iron oxide were added to a container containing 1270 g of
water and 180 g of a modified polycarboxylate ether type of
dispersant. The mixture was mechanically stirred for about 20
minutes and then added to a grinding mill. The sample was ground
for about 1 hour and a stable dispersion is obtained. The particle
size of the dispersed product was analyzed by Horiba LA-910
Particle Size Distribution Analyzer (PSDA). The average particle
size was 0.25 microns with a distribution range of 0.005 um to 1.5
um.
EXAMPLE 4
[0158] 2000 g yellow iron oxide and 44 g carbon black were added to
a container containing 2616.0 g of water and 340.0 g of a
commercially available solution of polycarboxylate ether
dispersant. The mixture was mechanically stirred for about 20
minutes and then added to a grinding mill. The sample was ground
for about 2.5 hours and a stable dispersion obtained. The particle
size of the dispersed product was analyzed by Horiba LA-910
Particle Size Distribution Analyzer (PSDA). The average particle
size was preferably 0.19 microns with a distribution range of 0.01
um to 1.1 um.
EXAMPLE 5
[0159] 2000 g yellow iron oxide and 198 g red iron oxide were added
to a container containing 2923.0 g of water and 374.0 g of a
commercially available solution of polycarboxylate ether
dispersant. The mixture was mechanically stirred for about 20
minutes and then added to a grinding mill. The sample was ground
for about 2.0 hours and a stable dispersion obtained. The particle
size of the dispersed product was analyzed by Horiba LA-910
Particle Size Distribution Analyzer (PSDA). The average particle
size was preferably 0.18 microns with a distribution range of 0.01
um to 1.2 um.
EXAMPLE 6
[0160] 1000 g yellow iron oxide and 124 g red iron oxide were added
to a container containing 1484.0 g of water and 202.0 g of a
commercially available polycarboxylate ether type of dispersant.
The mixture was mechanically stirred for about 20 minutes and then
added to a grinding mill. The sample was ground for about 1.2 hours
and a stable dispersion obtained. The particle size of the
dispersed product was analyzed by Horiba LA-910 Particle Size
Distribution Analyzer (PSDA). The average particle size was
preferably 0.18 microns with a distribution range of 0.04 um to 1.0
um.
EXAMPLE 7
[0161] Eight hundred and ninety grams of yellow iron oxide, 110 g
red iron oxide were added to a container containing 3000 g of water
and 200 g of a commercially available modified polycarboxylate
ether type of dispersant. The mixture was mechanically stirred for
about 20 minutes and then added to a grinding mill. The sample was
ground for about 1 hour and a stable dispersion obtained. The
particle size of the dispersed product was analyzed by Horiba
LA-910 Particle Size Distribution Analyzer (PSDA). The average
particle size was preferably 0.24 microns with a distribution range
of 0.010 um to 2.0 um.
EXAMPLE 8
[0162] Five hundred grams of organic pigment yellow PY65, 600 g of
organic pigments red PR23 and 15 g organic pigment blue PB 15 were
added to a container containing 3000 g of water and 450 g of a
modified polyether with pigment affinic groups dispersant. The
mixture is mechanically stirred for about 20 minutes and then added
to a grinding mill. The sample was ground for about 1 hour and a
stable dispersion obtained. The particle size of the dispersed
product was analyzed by Horiba LA-910 Particle Size Distribution
Analyzer (PSDA). The average particle size was 0.18 microns with a
distribution range of 0.0050 um to 2.0 um.
EXAMPLE 9
[0163] Eight hundred grams of organic pigment yellow PY 13 and 100
g of organic pigments red PR254 were added to a container
containing 4000 g of water and 500 g of a modified polymer with
pigment affinity group dispersant. The mixture was mechanically
stirred for about 20 minutes and then added to a grinding mill. The
sample was ground for about 1 hour and a stable dispersion was
obtained. The particle size of the dispersed product was analyzed
by Horiba LA-910 Particle Size Distribution Analyzer (PSDA). The
average particle size was 0.21 microns with a distribution range of
0.001 um to 2.0 um.
EXAMPLE 10
[0164] Five hundred grams of titanium dioxide is mixed with 450
grams of water and 50 grams of a modified polyacrylate polymer
dispersants. The mixture is mechanically stirred for 5 minutes. The
mixture is then placed in a grinding mill and ground for about 30
minutes. A stable dispersion is obtained with an average particle
size of 0.29 microns.
EXAMPLE 11
[0165] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by the Full Cell treatment
using a 1.1% MicroPro200 solution containing 0.73% micronized
copper carbonate as copper oxide and 0.37% quaternary ammonium
compound (dimethyl didecyl ammonium carbonate/bicarbonate), and
0.45% pigment solids from Example 1. The wood was initially placed
under a vacuum of 27'' Hg for 30 minutes followed by the addition
of the treating solution. The system was then pressurized for 30
minutes at a pressure of 110 lbs. per square inch. The resulting
wood, when dried, was colored reddish brown and protected against
wood destroying organisms.
EXAMPLE 12
[0166] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by a modified full cell
treatment using a 1.2% MicroPro200 solution containing 0.80%
micronized copper carbonate expressed as copper oxide and 0.40%
quaternary ammonium compound (dimethyl didecyl ammonium
carbonate/bicarbonate), and 0.50% pigment solids from Example 1.
The wood was initially placed under a vacuum of 22'' Hg for 7
minutes followed by the addition of the treating solution. The
system was then pressurized for 10 minutes at a pressure of 110
lbs. per square inch, followed with a 20 minutes final vacuum. The
resulting wood, when dried, was colored reddish brown and protected
against wood destroying organisms.
EXAMPLE 13
[0167] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by a modified full cell
treating process using a 1.0% MicroPro200 solution containing
0.667% micronized copper carbonate expressed as copper oxide and
0.333% quaternary ammonium compound (dimethyl didecyl ammonium
carbonate/bicarbonate), and 0.45% pigment solids from Example 5.
The wood was initially placed under a vacuum of 22'' Hg for 5
minutes followed by the addition of the treating solution. The
system was then pressurized for 5 minutes at a pressure of 110 lbs.
per square inch, followed by a 25 minutes final vacuum. The
resulting wood, when dried, was colored cedar-brown and protected
against wood destroying organisms.
EXAMPLE 14
[0168] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by a modified full cell
treating process using a 1.0% MicroPro200 solution containing
0.667% micronized copper carbonate expressed as copper oxide and
0.333% quaternary ammonium compound (dimethyl didecyl ammonium
carbonate/bicarbonate), and 0.48% pigment solids from Example 5 and
0.024% of
2-(((4-Methoxyphenyl)methylhydrazono)methyl)-1,3,3-trimethyl-3H-indolium
methyl sulphate dye. The wood was initially placed under a vacuum
of 22'' Hg for 5 minutes followed by the addition of the treating
solution. The system was then pressurized for 5 minutes at a
pressure of 110 lbs. per square inch, followed by a 25 minutes
final vacuum. The resulting wood, when dried, was colored brown and
protected against wood destroying organisms.
EXAMPLE 15
[0169] Southern Yellow Pine blocks (11/2''.times.2''.times.6'')
were simultaneously colored and preserved utilizing the Lowry Empty
Cell process using a 0.5% quaternary ammonium compounds based
preservative (dimethyl didecyl ammonium chloride) plus 0.49%
pigment solids from Example 2 and 0.030% hydroxyethyl cellulose
binder. The resulting wood was air dried to a 20% moisture content
and was colored a reddish brown color uniformly distributed on the
surface of the treated wood. The wood was exposed under an
accelerated tester (QUV) and found to exhibit great resistance to
UV photo-degradation. Laboratory accelerated agar test indicated
that the treated wood resist both attacks from brown rots and white
rots.
EXAMPLE 16
[0170] 50 grams of pigment concentrate from Example 5 were mixed
with 3950 g dimethyldidecylammonium carbonate (DDA Quat) water
solution containing 0.60% DDA Quat and 0.05% polyvinyl alcohol
resin. The solution was used to treat red pine and ponderosa pine
samples using the Full Cell process. The resulting wood was oven
dried at 120.degree. F. and was colored a cedar-brown color.
Outdoor exposure studies indicated that the treated samples were
resistant to biological deterioration and UV degradation.
EXAMPLE 17
[0171] Southern Yellow Pine blocks (1/2''.times.2''.times.6'') were
simultaneously colored and preserved using the Full Cell treatment
with a treating composition containing 0.10% copper
8-hydroxyquinolate plus 0.50% pigment dispersion from Example 1
with 0.005% a PVA type of binder. The Southern Yellow Pine blocks
were placed in a cylinder and a vacuum of 30'' Hg applied for 15
minutes, the treating composition was then added to the cylinder
and the system pressurized to 100 lbs. per square inch for 30
minutes. The resulting wood, when dried, was colored a reddish
brown and was protected against wood destroying organisms.
EXAMPLE 18
[0172] Douglas fir and Hem fir wood samples were colored a brown
color with a two-step process. Step I involved the treatment of
wood with 0.8% dimethyldidecylammonium carbonate solution using the
Full Cell process, followed by Step II treatment with a 1.0%
pigment solution from Example 5. The treated wood showed
bio-efficacy and color stability when exposed outside.
EXAMPLE 19
[0173] Southern pine, red pine and ponderosa pine samples were
colored a darker reddish brown color with a two-step process. Step
I involved the treatment of wood with a 2.0% pigment solution from
Example 2 plus 0.015% a commercially available binder using a
modified Full Cell process, followed by Step II treatment with a
composition containing 0.05% tebuconazole and 0.005% bifenthrin.
The treated samples demonstrated uniform surface coloration. The
samples also demonstrated bio-efficacy in a field test
evaluation.
EXAMPLE 20
[0174] Douglas fir and Hem fir samples were colored a darker
reddish brown color with a two-step process. Step I involved the
treatment of wood with a composition containing 1.0%
dimethyldidecylammonium carbonate solution using the Full Cell
process, followed by Step II treatment with a 1.0% pigment solution
from Example 2 plus 0.01% a commercially available binder. The
treated samples demonstrated uniform coloration on the surface and
bio-efficacy in a field test evaluation.
EXAMPLE 21
[0175] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by a modified full cell
treating process using a preservative solution containing 0.15%
tebuconazole and 0.03% bifenthrin and 0.50% pigment solids from
Example 1. The wood was initially placed under a vacuum of 22'' Hg
for 5 minutes followed by the addition of the treating solution.
The system was then pressurized for 5 minutes at a pressure of 110
lbs. per square inch, followed by a 25 minutes final vacuum. The
resulting wood, when dried, was colored reddish brown color and
protected against wood destroying organisms.
EXAMPLE 22
[0176] Southern Yellow Pine, (measuring 2''.times.6''.times.4') was
simultaneously colored and preserved by a modified full cell
treating process using a preservative solution containing 0.10%
tebuconazole and 0.02% bifenthrin and 0.50% pigment solids from
Example 5 The wood was initially placed under a vacuum of 22'' Hg
for 6 minutes followed by the addition of the treating solution.
The system was then pressurized for 7 minutes at a pressure of 110
lbs. per square inch, followed by a 25 minutes final vacuum. The
resulting wood, when dried, was colored cedar-brown and protected
against wood destroying organisms.
[0177] The foregoing examples are intended to be merely
illustrative and should not be construed or interpreted as being
restrictive or otherwise limiting of the present invention.
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